1. Field of the invention.
[0001] The present invention relates to a lithographic base. More particularly the present
invention relates to an improved adhesion of the hydrophilic lithographic layer to
the support of the lithographic base.
2. Background of the invention.
[0002] Lithography is the process of printing from specially prepared surfaces, some areas
of which are capable of accepting lithographic ink, whereas other areas, when moistened
with water, will not accept the ink. The areas which accept ink form the printing
image areas, generally hydrophobic areas, and the ink-rejecting areas form the background
areas, generally hydrophilic areas. In the art of photolithography, a photographic
material is made imagewise receptive to oily or greasy inks in the photo-exposed (negative-working)
or in the non-exposed areas (positive-working) on a hydrophilic background.
[0003] In the production of common lithographic printing plates, also called surface litho
plates or planographic printing plates, a lithographic base that has affinity to water
or obtains such affinity by chemical treatment is coated with a thin layer of a photosensitive
composition. Compositions for that purpose include light-sensitive materials such
as light-sensitive polymers, diazonium salts or resins, a photoconductive layer, a
silver halide emulsion etc. These materials are then image-wise exposed to actinic
radiation and processed in the appropriate manner so as to obtain a lithographic printing
plate.
[0004] In another embodiment, a silver precipitating (nucleating) agent is located in or
on top of the hydrophylic surface. An image is obtained on the precipitating layer
according to the silver salt diffusion transfer process by contacting said precipitating
layer with an exposed silver halide emulsion in the presence of a silver halide developing
agent and a silver halide solvent.
[0005] Several types of supports can be used for the manufacturing of a lithographic imaging
printing plate. Common supports are for example organic resin supports, e.g.polyesters,and
paper bases, e.g. polyolefin coated paper. These supports, if not sufficient hydrophilic
by themselves, are first coated with a hydrophilic layer forming the hydrophilic lithographic
background of the printing plate.
[0006] It is known to use as hydrophilic layer in these systems a layer containing polyvinyl
alcohol and hydrolyzed tetra(m)ethyl orthosilicate and preferably also silicium dioxide
and/or titanium dioxide as described in e.g. GB-P-1419512, FR-P-2300354, US-P-3971660
and 4284705, EP-A-405016 and 450199 and U.S. Serial No. 07/881,718.
[0007] In the use of such lithographic printing plates, an oleophilic (ink receptive) image
is present on a hydrophilic background. In printing, the printing plate is continuously
wetted with water and ink. The water is selectively taken up by the hydrophilic areas,
the ink by the oleophilic areas of the printing surface. During the printing process,
there occurs abrasion of the hydrophilic layer due to poor adhesion of this layer
to the support either point by point or over the whole surface. The adhesion of the
hydrophilic layer to the support is adversely influenced by a higher water adsorption
and thus a less rigid hydrophilic layer. Due to said abrasion the hydrophobic support
comes to the surface.This leads to ink acceptance in the non-printing areas, causing
staining of the plate.
[0008] In order to assure the adhesion of the hydrophilic layer to the support the support
is first coated with one or more subbing layers on which are coated in direct contact
therewith the hydrophilic layer. However said subbing layer(s) contain(s) organic
compounds, the irreproducibility of which leads to adhesion problems between the subbed
support and the hydrophilic layer. Furthermore a decreased water absorption resulting
in less emulgation with the ink and thereby an improved printing comfort and a sharper
printed image is still wanted. Still further an improved dry start-up is also wanted.
3. Summary of the invention.
[0009] It is an object of the present invention to provide a method for making a lithographic
base having on a support a hydrophilic layer of wich the adhesion to the support is
improved, especially qua reproducibility.
[0010] It is a further object of the present invention to provide a method for making a
lithographic base having on a support a hydrophilic layer of wich lithographic base
the water absorption is decreased.
[0011] It is still a further object of the present invention to provide a method for making
a lithographic base having on a support a hydrophilic layer of wich lithographic base
the dry upstart is improved.
[0012] Further objects of the present invention will become clear from the description hereinafter.
[0013] According to the present invention there is provided a method for obtaining a lithographic
base comprising on a hydrophobic support a hydrophilic layer contiguous to said support
containing a non-gelatineous hydrophilic (co)polymer or (co)polymer mixture, characterized
in that said hydrophobic support is treated with a plasma treatment with an applied
power density during the plasma treatment of at least 70 W min/m
2 before applying to said support said hydrophilic layer.
4. Detailed description of the present invention.
[0014] In the discipline of physics, the term "plasma" describes a partially ionized gas
composed of ions, electrons and neutral species. This state of matter may be produced
by the action of either very high temperatures, strong electric or radio frequency
(R.F.) electromagnetic fields. High temperature or "hot" plasmas are represented by
celestial light bodies, nuclear explosions and electric arcs. These are not suitable
for the modification of polymeric materials. Glow discharge plasmas are produced by
free electrons which are energized by an imposed direct current (DC) or R.F. electric
fields and then collide with neutral molecules. These neutral molecule collisions
transfer energy to the molecules and form a variety of active species including metastables,
free radicals and ions. These active species are chemically active and/or physically
modify the surface of materials and may therefore serve as the basis of new chemical
compounds and property modifications of existing compounds. A plasma is also called
the fourth aggregation phase. A plasma can be obtained by adding to a gas enough energy.
Plasma's which are used to functionalize the surface of a support are preferentially
created by means of an electric field. By exposing a polymeric support to a plasma,
there are introduced a variety on functional groups on the surface. The bulk of the
polymer remains unchanged.
[0015] Surprisingly it has been found that a lithographic base prepared by applying on a
hydrophobic support which is plasma treated under the conditions given above a non-gelatineous
hydrophilic layer contiguous to said support has improved properties qua adhesion
of the hydrophilic layer to the support, qua water absorption and qua dry upstart.
The power during the plasma treatment is preferably at least 120 W min/m
2, more preferably at least 175 W min/m
2.
[0016] Oower density is expressed by the following formula

wherein Pd stands for power density (in Watt min/m
2),
Ps stands for power supply ( in Watt),
WW stands for web width ( in m), and
Ls stands for line speed (in m/min).
[0017] Various hydrophobic supports may be used in the lithographic base in connection with
the present invention. Examples of such supports are organic resin supports e.g. cellulose
acetate films and polyolefin (e.g. polyethylene) coated paper. A preferred support
is polyethylene naphthalenedicarboxylate, a more preferred support is polyethylene
therephthalate film. Said support has preferably a thickness between 40 and 500 µm,
more preferably between 100 and 350 µm.
[0018] As hydrophilic (co)polymers in the hydrophilic layer of the lithographic base in
connection with the present invention a non-gelatineous, preferably a non-proteinic
(co)polymer is used. One may use, for example, homopolymers and copolymers of vinyl
alcohol, acrylamide, methylol acrylamide, methylol methacrylamide, acrylic acid, methacrylic
acid, hydroxyethyl acrylate, hydroxyethyl methacrylate or maleic anhydride/vinylmethylether
copolymers. The hydrophilicity of the (co)polymer or (co)polymer mixture used is the
same as or higher than the hydrophilicity of polyvinyl acetate hydrolyzed to at least
an extent of 80 percent by weight, preferably 95 percent by weight. Most preferably
polyvinyl alcohol is used in the hydrophilic layer in connection with the present
invention.
[0019] The hydrophilic layer of the lithographic base is preferably hardened. Preferred
hardening agents are those of the epoxide type, those of the ethylenimine type, those
of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, aldehydes e.g. formaldehyde,
glyoxal, and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin,
dioxan derivatives e.g. 2,3-dihydroxy-dioxan, active vinyl compounds e.g. 1,3,5-triacryloyl-hexahydro-s-triazine,
active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic
acids e.g. mucochloric acid and mucophenoxychloric acid. These hardeners can be used
alone or in combination. The binders can also be hardened with fast-reacting hardeners
such as carbamoylpyridinium salts of the type, described in US-P-4,063,952.
[0020] Preferably used hardening agents are tetraalkyl orthosilicate crosslinking agents.
Examples of tetraalkyl orthosilicate crosslinking agents are hydrolyzed tetraethyl
orthosilicate and hydrolyzed tetramethyl orthosilicate. The amount of tetraalkyl orthosilicate
crosslinking agent is at least 0.2 parts by weight per part by weight of hydrophilic
(co)polymer, preferably between 0.5 and 5 parts by weight, most preferably between
1 and 3 parts by weight.
[0021] The lithographic base can comprise only one hydrophilic layer. However the lithographic
base can also include more than one hydrophilic layer, the hydrophilic layer contiguous
to the support then being a part of the hydrophilic element of the lithographic base.
The hydrophilic layer or layers not contiguous to the hydrophobic support differs
from the hydrophilic layer contiguous to the hydrophobic support either in the nature
of the hydrophilic (co)polymer and/or the nature of the crosslinking agent and/or
the ratio between the hydrophilic (co)polymer and the crosslinking agent.
[0022] The hydrophilic layer or layers of the lithographic base preferably also contains
substances that increase the mechanical strength and the porosity of the layer. For
this purpose colloidal silica may be used. The colloidal silica employed may be in
the form of any commercially available water-dispersion of colloidal silica for example
having an average particle size upto 40 nm, e.g. 20 nm. In addition inert particles
of larger size than the colloidal silica can be added e.g. silica prepared according
to Stober as described in J. Colloid and Interface Sci., Vol. 26, 1968, pages 62 to
69 or alumina particles or particles having an average diameter of at least 100nm
which are particles of titanium dioxide or other heavy metal oxides. By incorporating
these particles the surface of the layer is given a uniform rough texture consisting
of microscopic hills and valleys, which serve as storage places for water in background
areas.
[0023] More details about suitable hydrophilic layers for use in connection with the present
invention can be found in e.g. GB-P-1419512, FR-P-2300354, US-P-3971660, US-P-4284705,
EP-A-405016, EP-A-450199 and U.S. Serial No. 07/881,718.
[0024] In a first method to obtain a lithographic plate the hydrophilic lithographic base
in accordance with the present invention may be coated with a thin layer of a heat-
or photosensitive composition. The heat- or photosensitive composition can also be
present partially or completely in the hydrophilic layer used in accordance with the
present invention. Compositions for that purpose include heat- or light-sensitive
substances such as heat-or light-sensitive polymers, diazonium salts or resins, quinonediazides,
photoconductive layers, silver halide emulsions etc. These materials are then imagewise
exposed to actinic radiation and processed in the appropriate manner so as to obtain
a lithographic printing plate.
[0025] According to one embodiment of the present invention an imaging element is prepared
by applying a layer comprising a photopolymerizable composition and a silver halide
emulsion layer to the lithographic base of the present invention. After imagewise
exposure of the silver halide emulsion layer and subsequent development a silver image
is obtained. The thus obtained silver image is subsequently employed as a mask for
the photopolymerizable composition during an overall exposure of the imaging element.
Finally the silver image and the non-exposed photopolymerizable composition are removed
so that a lithographic printing plate is obtained.
[0026] According to another embodiment of the present invention an imaging element is prepared
by applying a layer comprising a o-naphtoquinonediazide compound and an alkali soluble
resin to the lithographic base of the present invention. After imagewise exposure
of the photosensitive element and subsequent development a lithographic printing plate
is obtained.
[0027] More details about suitable o-naphtoquinonediazide containing lithographic compositions
for use in connection with the present invention can be found in e.g. EP-A-345016
and EP-A-508268. According to still another embodiment of the present invention
[0028] a lithographic printing plate is produced by the following steps :
(i) uniformly electrostatically charging a photoconductive layer, such as a coating
of zinc oxide photoconductive pigment dispersed in the hydrophilic layer of the present
invention by means of a corona-discharge, (ii) image-wise discharging said photoconductive
layer by exposing it to electromagnetic radiation to which it is sensitive, (iii)
applying electrostatically charged oleophilic toner particles to develop the resulting
electrostatic charge pattern and (iv) fixing the toner to the photoconductive layer.
Fixing is usually accomplished by the use of heat which causes the toner resin powder
to coalesce and adhere to the photoconductive layer.
[0029] More details about suitable electrophotographic lithographic compositions for use
in connection with the present invention can be found in e.g. US-P-2993787.
[0030] In a preferred embodiment there is provided a heat recording material comprising
the hydrophilic lithographic base of the present invention containing in homogeneously
distributed state throughout the entire hydrophilic layer hydrophobic thermoplastic
polymer particles having a softening or melting temperature of more than 30°C and
that are capable of coagulating when brought above their softening or melting temperature,
forming a hydrophobic agglomerate in the hydrophilic layer so that at these parts
the hydrophilic layer becomes sufficiently hydrophobic to accept a greasy ink in lithographic
printing wherein a dampening liquid is used.
[0031] Specific examples of hydrophobic polymer particles for use in connection with the
present invention are e.g.polyethylene,polyvinyl chloride, polymethyl(meth)acrylate,
polyethyl (meth)acrylate, polyvinylidene chloride, polyacrylonitrile, polyvinyl carbazole,
polystyrene etc. or copolymers thereof.
[0032] The molecular weight of the polymers may range from 5,000 to 1,000,000.
[0033] The hydrophobic particles may have a particle size from 0.01µm to 50µm, more preferably
between 0.05µm and 10µm and most preferably between 0.05µm and 2µm. The larger the
polymer particles are the less the resolving power of the heat recording material
will be.
[0034] The polymer particles are present as a dispersion in the aqueous coating liquid and
may be prepared by the methods disclosed in US-P-3.476.937. Another method especially
suitable for preparing an aqueous dispersion of the thermoplastic polymer particles
comprises:
- dissolving the hydrophobic thermoplastic polymer in an organic water immiscible solvent,
- dispersing the thus obtained solution in water or in an aqueous medium and
- removing the organic solvent by evaporation.
[0035] The amount of hydrophobic thermoplastic polymer particles contained in the hydrophilic
layer is preferably between 20% by weight and 65% by weight and more prerably between
25% by weight and 55% by weight and most preferably between 30% by weight and 45%
by weight. When too low amounts are used the hydrophobicity produced at the exposed
areas may be too small and as a consequence ink acceptance will be poor in these areas
whereas too large amounts of the hydrophobic thermoplastic polymer particles may result
in ink acceptance in the non-image areas due to a too large overall hydrophobicity
of the hydrophilic layer.
[0036] The above described heat recording material can be exposed by actinic radiation while
in contact with an original that contains a pattern of areas that are capable of converting
the radiation into heat at these areas so that the hydrophobic thermoplastic polymer
particles in the hydrophilic layer are softened or melted and coagulate in the exposed
areas thereby increasing the hydrobicity of the hydrophilic layer at these areas.
[0037] An especially suitable radiation is e.g. infrared or near infrared radiation. As
an original there may be used e.g. an imaged silver halide photographic material.
[0038] More details in connection with this embodiment can be found in e.g. US-P-3476937
and US-P-3971660.
[0039] In a further preferred embodiment there is provided a light-sensitive material comprising
a diazonium salt or resin, contained in homogeneously distributed state throughout
or preferably coated from a hydrophilic solution over the hydrophilic lithographic
base of the present invention.
[0040] Examples of low-molecular weight diazonium salt for use in the present invention
include: benzidine tetrazoniumchloride, 3,3'-dimethylbenzidine tetrazoniumchloride,
3,3'-dimethoxybenzidine tetrazoniumchloride, 4,4'-diaminodiphenylamine tetrazoniumchloride,
3,3'-diethylbenzidine tetrazoniumsulfate, 4-aminodiphenylamine diazoniumsulfate, 4-aminodiphenylamine
diazoniumchloride, 4-piperidino aniline diazoniumsulfate, 4-diethylamino aniline diazoniumsulfate
and oligomeric condensation products of diazodiphenylamine and formaldehyde.
[0041] Examples of diazo resins useful in the present invention include condensation products
of an aromatic diazonium salt as the light-sensitive substance. Such condensation
products are known and are described, for example, in DE-P-1214086. They are in general
prepared by condensation of a polynuclear aromatic diazonium compound, preferably
of substituted or unsubstituted diphenylamine-4-diazonium salts, with active carbonyl
compounds, preferably formaldehyde, in a strongly acid medium.
[0042] Said light-sensitive layer preferably also contains a binder e.g. polyvinyl alcohol
and may be applied to the lithographic base in a thickness of 0.2 µm to 5 µm. Said
presensitized imaging element advantageously contains water-soluble dyes such as rhodamines,
sudan blue, methylen blue, eosin or triphenylmethane dyes such as crystal violet,
victoria pure blue, malachite green, methylviolet and fuchsin or dye pigments which
are essentially water insoluble. Said dyes and/or dye pigments may be present in any
layer comprised on the support of said presensitized imaging element but are preferably
present in said hydrophilic layer and/or light-sensitive layer.
[0043] Exposure of the presensitized imaging element advantageously proceeds with ultraviolet
light optionally in combination with blue light in the wavelength range of 250 to
500 nm. Useful exposure sources are high or medium pressure halogen mercury vapour
lamps, e.g. of 1000 W. Since most lithography is done by the offset process, the imaging
element is exposed in such a way that the image obtained thereon is right reading.
The exposure may be an exposure using optics or a contact exposure.
[0044] The diazo resin or diazonium salts are converted upon exposure from water soluble
to water insoluble (due to the destruction of the diazonium groups) and additionally
the photolysis products of the diazo may induce an advancement in the level of crosslinking
of the polymeric binder or diazo resin, thereby selectively converting the surface,
in an image pattern, from water soluble to water insoluble. The unexposed areas remain
unchanged, i.e. water soluble.
[0045] When mounted on a printing press the printing plate is first washed with an aqueous
fountain solution. To prevent this fountain solution from being contaminated by residual
non-exposed diazo the unexposed diazo resin or diazonium salt should be removed from
the printing plate before mounting it on a printing press. This removal can be achieved
by rinsing or washing the imaging element with water or an aqueous solution.
[0046] More details in connection with this embodiment can be found in e.g. FR-P-2300354
, US-P-4284705 and EP-A-92203835.1.
[0047] In another method to obtain a lithographic plate the hydrophilic lithographic base
in accordance with the present invention is used as an image-receiving element for
a heat- or photosensitive composition.
[0048] In one embodiment the lithographic base in accordance with the present invention
may be used as a receiving element in a thermal transfer process where a hydrophobic
substance or composition is information-wise transferred from a donor element to said
lithographic base. Such a process is described in e.g. US-P-3,060,024, 3,085,488,
3,649,268 and EP-A-502,562.
[0049] According to a preferred embodiment of the present invention a toner image may be
transferred to the lithographic base of the present invention during an electrophotographic
process as disclosed in e.g. US-P-3,971,660 and EP-A-405,016.
[0050] According to the most preferred embodiment of the present invention a layer of physical
development nuclei may be applied to the lithographic base of the present invention.
Suitable physical development nuclei for use in accordance with the present invention
are e.g. colloidal silver, heavy metal sulphides e.g. silver sulphide, nickel sulphide,
palladium sulphide, cobalt sulphide, zinc sulphide, silver nickel sulphide etc. The
layer of physical development nuclei may contain a hydrophilic binder but preferably
does not contain a binder. The physical development nuclei contained in the image
receiving layer can also be present partially or completely in the hydrophilic layer
used in accordance with the present invention. A thus prepared element can be used
as the image-receiving element in a DTR-process. According to this method an image-wise
exposed photographic material comprising a silver halide emulsion layer is contacted
with said image-receiving element and developed in the presence of a silver halide
solvent e.g. thiosulphate or thiocyanate and one or more developing agents. Both elements
are subsequently separated and a silver image is formed in the layer of physical development
nuclei comprised on the image-receiving element. More details about this process for
obtaining a silver image in said receiving layer can be found in e.g. US-P-4.649.096
or EP-A-397926. Said silver image is oleophilic while the background of the image-receiving
element is oleophobic so that a lithographic printing plate results. It may however
be advantageous to improve the oleophilicity of the silver image by treating the silver
image with so-called hydrophobizing agents. US-P-3,776,728 describes the use of heterocyclic
mercapto-compounds, e.g. a 2-mercapto-1,3,4-oxadiazole derivative as hydrophobizing
agents, US-P-4,563,410 discloses hydrophobizing liquids containing one or more mercaptotriazole
or mercaptotetrazole derivatives.
[0051] The following examples illustrate the invention without however limiting it thereto.
All parts are by weight unless otherwise specified.
EXAMPLE 1
Preparation of the hydrophilic layer.
[0052] To 440 g of a dispersion containing 21.5 % TiO
2 (average particle size 0.3 to 0.5 um) and 2.5 % polyvinyl alcohol in deionized water
were subsequently added, while stirring, 250 g of a 5 % polyvinyl alcohol solution
in water, 105 g of a hydrolyzed 22 % tetramethyl orthosilicate emulsion in water and
22 g of a 10 % solution of a wetting agent. To this mixture was then added 183g of
deionized water and the pH was adjusted to pH=4.
Preparation of the lithographic base.
[0053] To five samples of polyethylene terephthalate support, treated as described in tabel
2 was applied the above mentioned hydrophilic layer to a wet coating thickness of
50 g/m
2, dried at 30°C and subsequently hardened by subjecting it to a temperature of 60°C
for 1 week. This layer was applied on the subbed side of the support for sample 1,
on a raw side of the support for sample 2 and on the plasma treated side for sample
3, 4 and 5. The influence of the pretreatment of the support on the adhesion, water
absorption of the lithographic bases and on a dry start-up is shown in table 2.
[0054] The adhesion was determined as follows:
- place the test strips in an apparatus containing five small balls, the strips are
transported through the apparatus
first ball 400 gram
second ball 600 gram
third ball 800 gram
fourth ball 1000 gram
fifth ball 1200 gram
- after the transport note the quantitative results as given in table 1.
Table 1
Evaluation |
Damage |
0 |
none |
0.5 |
very superficially |
1 |
damage not till the support |
2 |
locally damaged till the support |
3 |
fine scratch till the support |
4 |
broad scratch till the support (>1mm) |
5 |
very broad scratch till the support (>2mm) |
- move the sample 5 mm perpendicular on the moving direction and repeat the previous
step with balls of the following weight:
first ball 113 gram
second ball 163 gram
third ball 225 gram
fourth ball 282 gram
fifth ball 338 gram
- note again the results.
- move the sample 5 mm perpendicular on the moving direction and repeat the previous
step with balls of the following weight:
first ball 57 gram
second ball 85 gram
third ball 114 gram
fourth ball 142 gram
fifth ball 170 gram
- note again the results. Sum up the fifteen noted result for each sample.
The maximum value is 75. The lower the value of a sample the better the adhesion between
the support and the hydrophilic layer of the sample.
[0055] The amount of water absorption, expressed in g/m
2 was determined as follows:
- preserving the dry film for 15 minutes in a conditioning room at 20°C and 30 % RH,
- covering the backing topcoat layer of the dry film with a water impermeable tape,
- weighing the dry film,
- immersing the material in demineralized water of 24°C for 10 minutes,
- sucking up the excessive amount of water present on top of the outermost layers and
- immediately determining the weight of the wet film and
- calculating the measured weight differences between the wet and the dry film per square
meter.
[0056] The dry start-up is measured as follows:
- On the samples of the lithographic printing plate is drawn a rectangular of 30 mm
width with an ink accepting fluid.
- the samples are brought under identical conditions on a printing press Heidelberg
GTO52 with a Dahlgren 3-rol dampening unit and a compressible rubber blanket. The
ink used was Van Son Rubberbase RB2329 and the fountain used was Rotamatic 100%, sold
by Rotaprint.
- Start the press and let the Dahlgren dampening unit make contact with the lithographic
plate. After 10 revolutions, let the plate cylinder make contact with the inking cylinders
for five revolutions and start then printing.Print till 100 copies . The number given
is the first good copy, free of background staining.
Table 2
sample |
1 |
2 |
3 |
4 |
5 |
Subbing layer |
yes |
no |
no |
no |
no |
plasma treatment (W min/m2) |
0 |
0 |
70 |
140 |
200 |
adhesion |
8 |
75 |
10 |
8 |
1 |
water absorption |
2.2 |
- |
0.7 |
0.9 |
1 |
dry upstart |
>100 |
dela |
100 |
40 |
25 |
[0057] It is clear from the results that a lithographic base obtained from a support that
has undergone plasma treatment has one or more of the following advantages when compared
with a lithographic based obtained from a subbed support: adhesion, water absorption
and or dry start-up.